Quinophthalone dyestuffs

ABSTRACT

The invention relates to water-insoluble quinophthalone dyestuffs of the formula ##STR1## in which T represents W--Ar or ##STR2## and Ar denotes aryl, 
     W denotes oxygen, sulphur or N--R, 
     R denotes hydrogen or alkyl, 
     A denotes alkylene, O R 1  denotes alkyl or aryl, 
     R 2  denotes hydrogen or alkyl, 
     X denotes halogen, alkyl, alkoxy, nitro or acylamino, 
     Y denotes hydrogen or halogen, 
     Z denotes hydrogen, alkyl or halogen and 
     n denotes a number from 0 to 3 
     The new dyestuffs and their mixtures are distinguished by good affinity to polyester fibres and good general fastness properties.

The present invention relates to water-insoluble quinophthalone dyestuffs of the formula I ##STR3## in which T represents W-Ar or ##STR4## and Ar denotes aryl,

W denotes oxygen, sulphur or N-R,

R denotes hydrogen or alkyl,

A denotes alkylene,

R₁ denotes alkyl or aryl,

R₂ denotes hydrogen or alkyl,

X denotes halogen, alkyl, alkoxy, nitro or acylamino,

Y denotes hydrogen or halogen,

Z denotes hydrogen, alkyl or halogen and

n denotes a number from 0 to 3

As well as to their preparation, and their use for dyeing organic materials, especially for dyeing and printing hydrophobic synthetic fibre materials.

Suitable aryl radicals Ar and R₁ are naphthyl radicals and, preferably, phenyl radicals, which can optionally be monosubstituted, disubstituted or trisubstituted by halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenyl or phenoxy, but also CN, NO₂, S--CH₃, --COO--CH₃ and OH.

Suitable alkyl radicals R, X and Z are those with 1 to 4 C atoms, methyl and ethyl being preferred. The alkyl radical R can also be substituted, for example by CN, OH, methoxy or Cl.

Suitable alkoxy radicals X are those with 1 to 4 C atoms, methoxy and ethoxy being preferred.

Suitable acylamino radicals X are C₁ - to C₄ -alkylcarbonylamino radicals, acetylamino being preferred.

Halogen is preferably to be understood as chlorine and bromine.

Preferably, n represents 0, 1 or 2.

"Bulky" radicals such as, for example, t-butyl, are in positions where they do not cause steric hindrance, that is to say, for example, in the m- or p-position of a benzene ring.

Preferred dyestuffs of the formula I are those of the formula indicated, wherein

Ar denotes phenyl, chlorophenyl, dichlorophenyl, tolyl, methoxyphenyl, dimethylphenyl and trimethylphenyl,

X denotes Cl, Br, CH₃ or CH₃ O,

Y denotes H or Br,

Z denotes H,

W denotes O or NR,

R denotes H, CH₃ or C₂ H₅ and

n denotes 0, 1 or 2.

Particularly preferred dyestuffs of the formula I are those wherein

W represents NR.

Suitable alkylene radicals A are straight-chain or branched alkylene radicals, optionally interrupted by 0, with 2 to 6 C atoms, preferably --C₂ H₄ --, --C₃ H₆ -- and --C₄ H₈ --.

Suitable alkyl radicals R₁, R₂, X and Z are those with 1 to 4 C atoms, methyl and ethyl being preferred.

Preferred dyestuffs of the formula (I) are those of the formula indicated,

wherein

A represents --(CH₂)_(m) --,

X represents Cl, Br, CH₃ or CH₃ O,

Y represents H or Br,

Z represents H,

R₁ represents CH₃ or C₂ H₅,

R₂ represents H, CH₃ or C₂ H₅,

n represents 0, 1 or 2 and

m represents 2, 3 or 4.

The new dyestuffs of the formula I are obtained either by reacting phthalic acids or their anhydrides of the formulae II ##STR5## in which T and Z have the indicated meaning, with 3-hydroxyquinaldines of the formula III ##STR6## in which X and n have the indicated meaning and Q represents hydrogen or a carboxyl group, the optionally present carboxyl group Q being split off, or by reacting quinophthalone-sulphonic acid chlorides of the formula IV ##STR7## in which Z, X and n have the indicated meaning, in a manner which is in itself known with compounds of the formula ##STR8## with aryloxy compounds, arylthiol compounds or arylamines and optionally subsequently introducing a halogen atom, preferably a bromine atom, into the reaction products in the p-position to the quinoline nitrogen atom.

The condensation of the phthalic acids or their anhydrides (II) with the hydroxyquinaldines (III) is carried out in a manner which is in itself known (compare, for example, U.S. Pat. Nos. 3,023,213, 3,023,214 and 3,872,131 and British Patent Specification No. 693,686). The reaction is suitably carried out at temperatures of 170° to 240° C and in the presence of an organic solvent which is inert under the reaction conditions, such as, for example, dichlorotoluene, dichlorobenzene, tetrahydronaphthalene and various others.

Suitable reactants of the formula (II) are: phthalic acid-4-sulphonic acid phenyl ester, phthalic acid-4-sulphonic acid 2'-methyl-phenyl ester, phthalic acid-4-sulphonic acid 3'-methyl-phenyl ester, phthalic acid-4-sulphonic acid 4'-methyl-phenyl ester, phthalic acid-3-sulphonic acid phenyl ester, phthalic acid-3-sulphonic acid 3'-methyl-phenyl ester, phthalic acid-4-sulphonic acid 3'-ethyl-phenyl ester, phthalic acid-4-sulphonic acid 2',4'-dimethyl-phenyl ester, phthalic acid-4-sulphonic acid 2',5'-dimethyl-phenyl ester, phthalic acid-4-sulphonic acid 2'-isopropyl-phenyl ester, phthalic acid-4-sulphonic acid 4'-tert.-butylphenyl ester, phthalic acid-4-sulphonic acid 2'-methoxy-phenyl ester, phthalic acid 4-sulphonic acid 3'-methoxy-phenyl ester, phthalic acid-4-sulphonic acid 4'-methoxy-phenyl ester, phthalic acid-3-sulphonic acid 3'-methoxy-phenyl ester, phthalic acid-4-sulphonic acid 3'-ethoxy-phenyl ester, phthalic acid-4-sulphonic acid 2'-chloro-phenyl ester, phthalic acid-4-sulphonic acid 3'-chloro-phenyl ester, phthalic acid-4-sulphonic acid 4'-chloro-phenyl ester, phthalic acid-4-sulphonic acid 3'-bromo-phenyl ester, phthalic acid-4-sulphonic acid 3'-fluoro-phenyl ester, phthalic acid-4 -sulphonic acid 2',4'-dichloro-phenyl ester, phthalic acid-4-sulphonic acid 2',5'-dichloro-phenyl ester, phthalic acid-4-sulphonic acid 3'-nitro-phenyl ester, phthalic acid-4-sulphonic acid 4'-nitro-phenyl-ester, phthalic acid-4-sulphonic acid 2'-chloro-5'-methyl-phenyl ester, phthalic acid 4-sulphonic acid 3',5'-dimethyl-phenyl ester, phthalic acid-4-sulphonic acid 1'-naphthyl ester, phthalic acid-4-sulphonic acid 2'-naphthyl ester, phthalic acid-4-sulphonic acid 3'-methyl-4'-methylmercapto-phenyl ester, phthalic acid-4-sulphonic acid 3'-carbethoxy-phenyl ester, phthalic acid-4-sulphonic acid 3'-cyanophenyl ester and phthalic acid-4-thiosulphonic acid S-phenyl ester; phthalic acid-4-sulphonic acid N-phenyl-amide, phthalic acid-4-sulphonic acid N-methyl-N-phenyl-amide, phthalic acid-3-sulphonic acid N-phenyl-amide, phthalic acid-4-sulphonic acid N-2'-methyl-phenyl-amide, phthalic acid-4-sulphonic acid N-3'-methyl-phenyl-anide, phthalic acid-3-sulphonic acid N-3'-methyl-phenyl-amide, phthalic acid-4-sulphonic acid N-4'-methyl-phenyl-amide, phthalic acid-4-sulphonic acid N-3'-methyl-phenyl-N-ethylamide, phthalic acid-4-sulphonic acid N-3'-ethyl-phenyl-amide, phthalic acid-4-sulphonic acid N-2',4'-dimethyl-phenyl-amide, phthalic acid-4-sulphonic acid N-2',5°-dimethyl-phenyl-amide, phthalic acid-4-sulphonic acid 3',5'-dimethyl-phenyl-amide, phthalic acid-4-sulphonic acid N-2'-isopropyl-phenyl-amide, phthalic acid-4-sulphonic acid N-4'-tert.-butyl-phenyl-amide, phthalic acid-4-sulphonic acid N-2'-methoxy-phenyl-amide, phthalic acid-4-sulphonic acid N-3'-methoxy-phenyl-amide, phthalic acid-4-sulphonic acid N-4'-methoxy-phenyl-amide, phthalic acid-3-sulphonic acid N-3'-methoxy-phenyl-amide, phthalic acid-4-sulphonic acid N-2',4'-dimethoxy-phenyl-amide, phthalic acid-4-sulphonic acid N-2',5'-dimethoxy-phenyl-amide, phthalic acid-4-sulphonic acid N-3'-ethoxy-phenyl-amide, phthalic acid-4-sulphonic acid N-2'-chlorophenyl-amide, phthalic acid-4-sulphonic acid N-3'-chlorophenyl-amide, phthalic acid-4-sulphonic acid N-4'-chloro-phenyl-amide, phthalic acid-4-sulphonic acid N-3'-bromophenyl-amide, phthalic acid-4-sulphonic acid N-3'-fluoro-phenyl-amide, phthalic acid-4-sulphonic acid N-3'-trifluoromethyl-phenylamide, phthalic acid-4-sulphonic acid N-2',4'-dichloro-phenylamide, phthalic acid-4-sulphonic acid N-2',5'-dichloro-phenylamide, phthalic acid-4-sulphonic acid N-2'-chloro-5'-methylphenyl-amide, phthalic acid-4-sulphonic acid N-3'-nitrophenyl-amide, phthalic acid-4-sulphonic acid N-3'-cyanophenyl-amide, phthalic acid-4-sulphonic acid N-4'-carbomethoxy-phenyl-amide, phthalic acid-4-sulphonic acid N-2',6'-dimethyl-phenyl-amnide, phthalic acid-4-sulphonic acid N-1'-naphthyl-amide, phthalic acid-4-sulphonic acid N-3'-hydroxymethyl-phenyl-amide; phthalic acid-4-methoxyethylsulphamide phthalic acid-4-N-ethoxyethyl-sulphamide, phthalic acid-4-N-propoxyethyl-sulphamide, phthalic acid-4-N-butoxyethyl-sulphamide, phthalic acid-4-N-hexoxyethylsulphamide, phthalic acid-4-N-methoxypropyl-sulphamide, phthalic acid-4-N-ethoxypropyl-sulphamide, phthalic acid-4-N-propoxypropyl-sulphamide, phthalic acid-4-N-isopropoxypropylsulphamide, phthalic acid-4-N-butoxypropyl-sulphamide, phthalic acid-4-N-hexoxypropyl-sulphamide, phthalic acid-4-N-methoxypropyl-N-methyl-sulphamide, phthalic acid-4-N-ethoxypropyl-N-methyl-sulphamide, phthalic acid-4-N-methoxypropyl-N-ethyl-sulphamide, phthalic acid-3-N-methoxypropyl-sulphamide, phthalic acid-3-N-ethoxypropyl-sulphamide, phthalic acid-3-N-ethoxypropyl-N-methyl-sulphamide and phthalic acid-4-N-methoxypropyl-sulphamide or their anhydrides.

These compounds can easily be prepared in the usual manner from phthalic acid-4-sulphonic acid chloride or phthalic acid-3-sulphonic acid chloride by reaction with the corresponding amines, phenols or thiophenols.

Examples of suitable starting compounds of the formula (III) are 3-hydroxyquinaldine, 3-hydroxyquinaldine-4-carboxylic acid, 3-hydroxy-5,7-dimethyl-quinalidine, 3-hydroxy-6,8-dichloro-quinaldine, 3-hydroxy-6-bromo-quinaldine and 3-hydroxy-6,8-dibromo-quinaldine.

The quinophthalonesulphonic acids have not previously been described; these compounds are obtained in a manner which is in itself known by condensation of phthalic acid-4 -sulphonates or -3-sulphonates or their anhydrides with appropriate 3-hydroxyquinaldines.

The conversion of the quinophthalonesulphonic acids or their salts ot the acid chlorides (IV) is also carried out in a manner which is in itself known, with the aid of inorganic acid chlorides, such as thionyl chloride, phosphorus pentachloride or phosphorus oxychloride, if appropriate in the presence of inert organic solvents. The reaction of the compounds (I) with amines to give the sulphamides according to the invention is also known in principle (compare DT-OS (German Published Specification No.) 2,034,264 = British Patent Specification No. 1,363,131).

The post-halogenation, preferably post-bromination, of the reaction products which in the abovementioned processes may have to be carried out to introduce the substituent Y = halogen can also be effected in accordance with known methods, for example in accordance with the data in German Patent Specification No. 1,229,663 and in British Patent Specification No. 1,263,345, by treating dyestuffs of the formula (I), in which Y = H, with halogen, preferably bromine, if appropriate at elevated temperature in inert organic solvents.

The new dyestuffs of the formula (I), optionally also mixed with one another or with dyestuffs of similar structure such as, for example, those of the formula I, in which

the group -W-Ar is replaced by the radical ##STR9## wherein A represents a C₂ -C₆ -alkylene radical and

B represents C₁ -C₄ -alkyl and

R has the abovementioned meaning,

are outstandingly suitable for dyeing organic materials, especially for dyeing and/or printing synthetic hydrophobic fibre materials from an aqueous liquor. They are dyed or printed in accordance with the methods customary for the fibres. Cellulose triacetate fibres and polyamide fibres can be dyed at about 100° C from aqueous liquors, if appropriate in the presence of customary auxiliaries. When dyeing fibres of aromatic polyesters, for example polyethylene glycol terephthalate, the customary carriers can be added to the dyebath, or the dyeing can be carried out without added carrier at 120°-130° C under pressure. The dyeings can also be fixed by a brief heat treatment at 190°-220° C. It is advantageous to bring the dyestuffs, before use, to a finely divided state in accordance with the customary methods, for example by grinding or kneading, preferably in the presence of customary dispersing agents.

The new dyestuffs and their mixtures are distinguished by good affinity to polyester fibres and good general fastness properties.

In the Examples which follow, the parts indicated are parts by weight and the degrees are degrees centigrade.

In the Examples which follow, the parts indicated are parts by weight and the degrees are degrees centigrade.

EXAMPLE 1

19.3 parts of phthalic acid-4-sulphonic acid phenyl ester (obtained by reaction of phthalic acid-4-sulphonic acid chloride with sodium phenolate) are convertd to the anhydrideby heating in 260 parts of o-dichlorobenzene to 175°-180°. In the course thereof, the water produced is distilled off together with 60 parts of o-dichlorobenzene 12 parts of benzoic acid and 10.15 parts of 3-hydroxyquinaldine-4-carboxylic acid are then introduced under a nitrogen atmosphere and the reaction mixture is stirred at 170°-180° until the formation of dyestuff is complete; in the course thereof, again, the water produced is distilled off together with a little o-dichlorobenzene. Thereafter the residual o-dichlorobenzene is largely distilled off under reduced pressure, the residue which remains is diluted with 80 parts of methanol, and the mixture is cooled to 15°-20°. The reaction product which has separated out is filtered off and washed with methanol. After drying, 19.5 parts of the dyestuff of the formula ##STR10## are obtained. The dyestuff gives a reddish-tinged yellow dyeing of good fastness properties on polyester materials.

EXAMPLE 2

20.1 parts of phthalic acid-4-sulphonic acid 3'-methyl-phenyl ester (obtained by reaction of phthalic acid-4-sulphonic acid chloride with the sodium salt of m-cresol) are introduced into 200 parts of 2,4-dichlorotoluene and converted to the anhydride by heating to 175°-180°. In the course thereof, the water produced is distilled off together with 50 parts of 2,4-dichlorotoluene. Thereafter, 12 parts of benzoic acid and 7.95 parts of 3-hydroxyquinaldine are added to the melt under a nitrogen atmosphere and the reaction mixture is stirred at 170°-180° C until the reaction is complete. In the course thereof, again, the water produced is distilled off together with a little 2,4-dichlorotoluene.

After removing the residual solvent by distillation under reduced pressure, the residue which remains is stirred with 80 parts of methanol, the mixture is cooled to 15°-20° and filtered, and the filter residue is rinsed with methanol. After drying, 19.7 parts of the dyestuff of the formula ##STR11## are obtained. The dyestuff gives a reddish-tinged yellow dyeing of good fastness properties on polyester materials.

EXAMPLE 3-36

Analogously to the description in Examples 1 and 2, tje 3'-hydroxyquinopthalone dyestuffs of the general formula ##STR12## listed in the Table which follows are obtained on using the corresponding phthalic acid derivatives or their anhydrides:

    __________________________________________________________________________                                   Shade on                                         Example                                                                             X    n   Z               polyester                                        __________________________________________________________________________      3   H    --                                                                               4-                                                                                ##STR13##      reddish-tinged yellow                             4   H    --                                                                               4-                                                                                ##STR14##      golden yellow                                     5   H    --                                                                               3-                                                                                ##STR15##      yellow                                            6   H    --                                                                               3-                                                                                ##STR16##      yellow                                            7   5',7'-CH.sub.3                                                                      2 4                                                                                 ##STR17##      reddish-tinged yellow                             8   6',8'-Cl                                                                            2 4                                                                                 ##STR18##      reddish-tinged yellow                             9   6'-Br                                                                               1 4                                                                                 ##STR19##      reddish-tinged yellow                            10   5',7'-CH.sub.3                                                                      2 4                                                                                 ##STR20##      reddish-tinged yellow                            11   H    --                                                                               4                                                                                 ##STR21##      yellow                                           12   H    --                                                                               4                                                                                 ##STR22##      yellow                                           13   H    --                                                                               4                                                                                 ##STR23##      yellow                                           14   H    --                                                                               4                                                                                 ##STR24##      yellow                                           15   H    --                                                                               4                                                                                 ##STR25##      yellow                                           16   H    --                                                                               4                                                                                 ##STR26##      reddish-tinged yellow                            17   H    --                                                                               4                                                                                 ##STR27##      reddish-tinged yellow                            18   H    --                                                                               3                                                                                 ##STR28##      yellow                                           19   H    --                                                                               4                                                                                 ##STR29##      yellow                                           20   H    --                                                                               4                                                                                 ##STR30##      yellow                                           21   H    --                                                                               4                                                                                 ##STR31##      yellow                                           22   H    --                                                                               4                                                                                 ##STR32##      yellow                                           23   H    --                                                                               4                                                                                 ##STR33##      yellow                                           24   H    --                                                                               4                                                                                 ##STR34##      yellow                                           25   H    --                                                                               4                                                                                 ##STR35##      yellow                                           26   H    --                                                                               4                                                                                 ##STR36##      yellow                                           27   H    --                                                                               4-                                                                                ##STR37##      yellow                                           28   H    --                                                                               4                                                                                 ##STR38##      yellow                                           29   H    --                                                                               4                                                                                 ##STR39##      yellow                                           30   H    --                                                                               4                                                                                 ##STR40##      golden yellow                                    31   H    --                                                                               4                                                                                 ##STR41##      reddish-tinged yellow                            32   H    --                                                                               4                                                                                 ##STR42##      yellow                                           33   H    --                                                                               4                                                                                 ##STR43##      yellow                                           34   H    --                                                                               4                                                                                 ##STR44##      yellow                                           35   H    --                                                                               4                                                                                 ##STR45##      yellow                                           36   H    --                                                                               4                                                                                 ##STR46##      yellow                                           __________________________________________________________________________

EXAMPLE 37

22 parts of phthalic acid-4-sulphonic acid N-3'-methyl-phenyl-amide (obtained by reaction of phthalic acid-4-sulphonic acid chloride with m-toluidine) are converted to the anhydride by heating in 260 parts of o-dichlorobenzene to 175°-180°. In the course thereof, the water produced is distilled off together with 60 parts of o-dichlorobenzene. 12 parts of benzoic acid and 10.15 parts of 3-hydroxyquinaldine-4-carboxylic acid are then introduced under a nitrogen atmosphere and the reaction mixture is stirred at 170°-180° until dyestuff formation is complete; in the course thereof, again, the water produced is distilled off together with a little o-dichlorobenzene. Thereafter, the residual o-dichlorobenzene is removed by vacuum distillation and the residue which remains is diluted with methanol and cooled to 15°-20°. The reaction product which has separated out is filtered off and washed with methanol. After drying, 20.5 parts of the dyestuff of the formula ##STR47## are obtained. The dyestuff gives a golden yellow dyeing of good fastness properties on polyester materials.

EXAMPLE 38

18 parts of phthalic acid-4-sulphonic acid N-phenylamide (obtained by reaction of phthalic acid-4-sulphonic acid chloride with aniline) are introduced into 200 parts of 2,4-dichlorotoluene and converted to the anhydride by heating to 175°-180°. In the course thereof, the water produced is distilled off together with 50 parts of 2,4-dichlorotoluene. 12 parts of benzoic acid and 7.95 parts of 3-hydroxyquinaldine are then added to the melt under a nitrogen atmosphere and the reaction mixture is stirred at 170° to 180° until formation of the dyestuff is complete. In the course thereof, again, the water produced is distilled off together with a little 2,4-dichlorotoluene. After removing the residual solvent by distillation under reduced pressure, the residue which remains is stirred with 80 parts of methanol, the mixture is cooled to 15°-20° and filtered, and the filter residue is rinsed with methanol. After drying, 18 parts of the dyestuff of the formula ##STR48## are obtained. The dyestuff gives a golden yellow dyeing of good fastness properties on polyester materials.

EXAMPLE 39

21 parts of phthalic acid-4-sulphonic acid N-3'-methoxy-phenyl-amide (obtained by reaction of phthalic acid-4-sulphonic acid chloride with 3-methoxy-aniline) and 10.15 parts of 3-hydroxyquinaldine-4-carboxylic acid are introduced into 200 parts of 2,4-dichlorotoluene. The reaction mixture is heated to 180°-190° and is stirred at this temperature until dyestuff formation is complete. In the course thereof, the water produced is distilled off together with about 60 parts of dichlorotoluene. After removing the residual solvent by vacuum distillation, the residue which remains is diluted with methanol and the dyestuff which has separated out is filtered off at 15°-20°, washed with methanol and dried. 17.7 parts of the dyestuff of the formula ##STR49## are obtained. The dyestuff gives a golden yellow dyeing of good fastness properties on polyester materials.

EXAMPLE 40-76

Analogously to the description in Examples 37-39, the 3'-hydroxyquinophthalone dyestuffs of the general formula ##STR50## listed in the Table which follows are obtained on using the corresponding phthalic acid derivatives or their anhydrides:

    ______________________________________                                                                                  Shade                                 Ex.  X        n          Z               on PE                                 ______________________________________                                         40   H        --    4-                                                                                   ##STR51##      yellow                                41   H        --    4-                                                                                   ##STR52##      yellow                                42   H        --    4-                                                                                   ##STR53##      yellow                                43   H        --    4-                                                                                   ##STR54##      yellow                                44   H        --    3-                                                                                   ##STR55##      golden yellow                         45   H        --    3-                                                                                   ##STR56##      yellow                                46   H        --    4-                                                                                   ##STR57##      yellow                                47   H        --    3-                                                                                   ##STR58##      yellow                                48   5',7'-CH.sub.3                                                                          2     4-                                                                                   ##STR59##      yellow                                49   6'-Br    1     4-                                                                                   ##STR60##      yellow                                50   H        --    4-                                                                                   ##STR61##      yellow                                51   H        --    4                                                                                    ##STR62##      yellow                                52   H        --    4                                                                                    ##STR63##      yellow                                53   H        --    4                                                                                    ##STR64##      yellow                                54   H        --    4-                                                                                   ##STR65##      yellow                                55   H        --    4                                                                                    ##STR66##      yellow                                56   H        --    4                                                                                    ##STR67##      yellow                                57   H        --    4                                                                                    ##STR68##      yellow                                58   H        --    4                                                                                    ##STR69##      yellow                                59   H        --    4                                                                                    ##STR70##      golden yellow                         60   6',8'-Cl 2     4                                                                                    ##STR71##      yellow                                61   H        --    4                                                                                    ##STR72##      yellow                                62   H        --    4                                                                                    ##STR73##      yellow                                63   H        --    4                                                                                    ##STR74##      yellow                                64   H        --    4                                                                                    ##STR75##      yellow                                65   H        --    4                                                                                    ##STR76##      yellow                                66   H        --    4                                                                                    ##STR77##      yellow                                67   H        --    4                                                                                    ##STR78##      yellow                                68   H        --    4-                                                                                   ##STR79##      yellow                                69   H        --    4                                                                                    ##STR80##      yellow                                70   H        --    4                                                                                    ##STR81##      yellow                                71   H        --    4                                                                                    ##STR82##      yellow                                72   H        --    4                                                                                    ##STR83##      yellow                                73   H        --    4                                                                                    ##STR84##      yellow                                74   H        --    4                                                                                    ##STR85##      yellow                                75   H        --    4                                                                                    ##STR86##      yellow                                76   H        --    4                                                                                    ##STR87##      yellow                                ______________________________________                                    

EXAMPLE 77

5-parts of 3-hydroxy-quinophthalone-4'-N-phenylsulphamide (prepared according to Example 38) are suspended in 200 parts of glacial acetic acid and 4.5 parts of bromine are added. The reaction mixture is stirred for 15 hours at 15°-25° and is then filtered. The residue is washed with bisulphite solution and water and dried. 5.4 g of the dyestuff of the formula ##STR88## are obtained. The dyestuff gives yellow dyeings of good fastness properties on polyester materials.

EXAMPLE 78

7.5 parts of 3-hydroxy-quinophthalone-4-sulphonic acid phenyl ester (obtained according to Example 1) are suspended in 300 parts of glacial acetic acid and 7 parts of bromine are added. The reaction mixture is stirred for 15 hours at room temperature and is then filtered. The filter residue is washed with bisulphite solution and water and dried. 8.4 parts of the dyestuff of the formula ##STR89## which contains 15% of bromine are obtained.

The dyestuff gives yellow dyeings of good fastness properties on polyester materials.

EXAMPLE 79

1 part of the dyestuff mentioned in Example 1, which has beforehand been brought to a finely divided state in the presence of dispersing agents, is dispersed in 400 parts of water. 100 parts of polyester fibres (polyethylene terephthalate) are dyed in the resulting dyebath in the presence of 15 parts of o-cresotic acid methyl ester as a carrier, for 120 minutes at the boil. A strong reddish-tinged yellow dyeing of good fastness properties, especially of good fastness to light and sublimation, is obtained.

Clear yellow dyeings, which are also strong, are obtained if instead of the dyestuff mentioned in Example 1, 1 part of the dyestuffs obtained in Examples 2 to 6, 11, 14, 16 to 18, 20 to 22, 30, 31, 37, 39, 40, 41, 44, 45, 51, 54 to 56, 58, 59, 61 and 62 is employed in the above dyeing procedure.

EXAMPLE 80

100 parts of polyester fibres (polyethylene terephthalate) are dyed with 1 part of the dyestuff mentioned in Example 38, which has beforehand been brought to a finely divided state with the customary auxiliaries, in 3,000 parts of water for one hour at 125°-130° under pressure. A clear golden yellow dyeing of good fastness properties is obtained.

If instead of the dyestuff mentioned in Example 38, 1 part of the dyestuffs described in Examples 7, 12, 13, 15, 23 to 29, 43, 46 to 50, 52, 53, 63 to 67, 71 to 73 or 75 is used, clear yellow dyeings of good fastness properties are again obtained.

EXAMPLE 81

A woven fabric of polyester fibres (polyethylene terephthalate) is impregnated on a padder with a liquor which contains, per liter, 20 g of the dyestuff described in Example 1, which has beforehand been brought to a finely divided state in the presence of dispersing agents. The fabric is squeezed off to a weight pick-up of 70% and is dried at 100°. To fix the dyeing, the fabric is then treated for 60 seconds at 190°-220° with hot air, rinsed, washed hot and dried. A clear golden yellow dyeing of good fastness properties is obtained.

If instead of the abovementioned dyestuff, 20 g of the dyestuffs prepared according to Examples 8 to 10, 19, 32 to 36, 41, 57 to 60 or 68 to 78 are used, clear yellow dyeings of good fastness properties are again obtained.

EXAMPLE 82

A previously cleaned and thermoset woven fabric of polyethylene terephthalate is printed with a paste consisting of the following components: 20 of dyestuff obtained according to Example 1, in a finely divided form, 520 g of water, 450 g of 1:2 crystal gum and 10 g of cresotic acid methyl ester. To fix the dyestuff, the printed and dried goods are treated with hot air for 40 seconds at 200°. After soaping, rinsing and drying, a clear golden yellow print of good fastness properties is obtained.

Clear prints of good fastness properties are also obtained if instead of the abovementioned dyestuff, 20 g of rhe dyestuffs prepared according to Examples 2, 3, 5 to 7, 16 to 18, 37 to 40 or 44 to 49 are used.

EXAMPLE 83

100 parts of a polyamide woven fabric are dyed with 1 part of the dyestuff described in Example 1, which has beforehand been brought to a finely divided state in accordance with the customary methods, in 4,000 parts of water for 1 hour at 100°. The fabric is subsequently rinsed warm and cold, and dried. A yellow dyeing of good fastness to washing and to light is obtained.

EXAMPLE 84

A dyebath is prepared with 1 part of the dyestuff mentioned in Example 37, which has beforehand been brought to a finely divided state using the auxiliaries customary for this purpose, 6 parts of fat alcohol-suphonate and 3,000 parts of water and 100 parts of cellulose triacetate fibres are dyed in this bath for 1 hour at 100°. A yellow dyeing of good fastness to washing, thermosetting and light is obtained.

EXAMPLE 85

A mixture of 1 part each of the dyestuffs prepared according to Examples 39 and 56, which has beforehand been brought to a finely divided state in the presence of dispersing agents, is dispersed in 400 parts of water. 100 parts of polyester fibres (polyethylene terephthalate) are dyed in the resulting dyebath, in the presence of 15 parts of o-cresotic acid method ester as a carrier, for 120 minutes at the boil. A very strong golden yellow dyeing of good fastness properties is obtained.

Comparable strong golden yellow dyeings are obtained if the procedure described above is followed, but 2 parts of a dyestuff mixture of the dyestuffs described in Examples 39 and 56 are used whilst varying the ratio of the two dyestufffs from 2:8 to 8.2 and especially from 4:6 to 6:4.

Comparably strong polyester dyeings are obtained if, in the above Example, 2 parts of a mixture of the dyestuffs from the following Examples are employed:

    ______________________________________                                                            Mixing ratio                                                Dyestuff from                                                                            and    Dyestuff from                                                                              from    to                                        ______________________________________                                         Example 39       Example 59  2 : 8   8 : 2                                     Example 37       Example 59  2 : 8   8 : 2                                     Example  1       Example 37  2 : 8   8 : 2                                     Example  1       Example 59  2 : 8   8 : 2                                     Example  1       Example 2   2 : 8   8 : 2                                     Example 17       Example 37  2 : 8   8 : 2                                     Example  2       Example 17  2 : 8   8 : 2                                     ______________________________________                                    

EXAMPLE 86

A mixture of 0.5 part of the quinophthalone dyestuff obtained according to Example 38 and 0.5 part of 3-hydroxy-quinophthalone-4'-N-dimethyl-sulphamide (described in British Patent Specification No. 1,363,131, Example 262, which has beforehand been brought to a finely divided state in the presence of dispersing agents, is dispersed in 400 parts of water. 100 parts of polyester fibres (polyethylene terephthalate) are dyed in the resulting dyebath in the presence of 15 parts of o-cresotic acid methyl ester as the carrier for 120 minutes at the boil. A very strong yellow dyeing of good fastness properties is obtained.

Comparable yellow dyeings are obtained if the procedure described above is followed but a mixture of the two dyestuffs in the ratio of 4 : 6 to 6 : 4 is used.

Comparable polyester dyeings are obtained if, in the above Example, 1 part of a mixture of the dyestuffs of the Examples which follow, in the mixing ratio indicated, is employed:

    ______________________________________                                         Dyestuff         Dyestuff                                                      according        according to                                                  to               British Patent                                                present          Specification                                                                              Mixing ratio                                      Application                                                                              and    1,363,131   from    to                                        ______________________________________                                         Example 38       Example 261 4 : 6   6 : 4                                     Example 39       Example 263 4 : 6   6 : 4                                     Example 56       Example 262 4 : 6   6 : 4                                     ______________________________________                                    

EXAMPLE 87

17.5 parts of phthalic acid-4-N-methoxypropylsulphamide (obtained by reaction of phthalic acid-4-sulphonic acid chloride with 3-methoxypropylamine) are converted into the anhydride by heating to 175°-180° in 260 parts of odichlorobenzene. In the course thereof, the water produced is distilled off together with 60 parts of o-dichlorobenzene. 12 parts of benzoic acid and 10.15 parts of 3-hydroxyquinaldine-4-carboxylic acid are then introduced under a nitrogen atmosphere and the reaction mixture is stirred at 170°-180° until the formation of the dyestuff is complete; in the course thereof, again, the water produced is distilled off together with a little o-dichlorobenzene. Thereafter the remaining o-dichlorobenzene is largely distilled off under reduced pressure, the residue which remains is diluted with 80 parts of methanol, and the mixure is cooled to 15 -20°. The reaction product which has separated out is filtered off and ashed with methanol. After drying, 16.6 parts of the dyestuff of the formula ##STR90## are obtained. On polyester materials the dyestuff gives a golden yellow dyeing of good fastness properties.

EXAMPLE 88

18.2 parts of phthalic acid-4-N-ethoxypropylsulphamide (obtained by reaction of phthalic acid-4-sulphonic acid chloride with 3-ethoxypropylamine) are introduced into 200 parts of 2,4-dichlorotoluene and converted to the anhydride by heating to 175°-180°. In the course thereof, the water produced is distilled off together with 50 parts of 2,4-dichlorotoluene. Thereafter, 12 parts of benzoic acid and 7.95 parts of 3-hydroxyquinaldine are added to the melt under a nitrogen atmosphere and the reaction mixture is stirred at 170°-180° until the formation of the dyestuff is complete. In the course thereof, again, the water produced is distilled off together with a little 2,4-dichlorotoluene. After removing the residual solvent by distillation under reduced pressure the residue which remains is stirred with 80 ml of methanol, the mixture is cooled to 15°-20° and filtered, and the filter residue is rinsed well with methanol. After drying, 16 parts of the dyestuff of the formula ##STR91## are obtained. On polyester materials, the dyestuff gives a reddish-tinged yellow dyeing of good fastness properties.

EXAMPLES 89-109

Analogously to the description in Examples 1 and 2, the 3-hydroxyquinophthalone dyestuffs of the general formula ##STR92## listed in the Table which follows are obtained on using the corresponding phthalic acid derivatives or their anhydrides:

    __________________________________________________________________________                                     Shade on                                       Example                                                                             X    n Z                   polyester                                      __________________________________________________________________________     89   H    --                                                                               4-SO.sub.2 NH(CH.sub.2).sub.3OC.sub.4 H.sub.9                                                      neutral yellow                                 90   H    --                                                                                ##STR93##          yellow                                         91   H    --                                                                               4-SO.sub.2 NH(CH.sub.2).sub.2OCH.sub.3                                                             golden yellow                                  92   H    --                                                                               4-SO.sub.2 NH(CH.sub.2).sub.2OC.sub.2 H.sub.5                                                      golden yellow                                  93   H    --                                                                               4-SO.sub.2 NH(CH.sub.2).sub.2OC.sub.4 H.sub.9                                                      medium yellow                                  94   H    --                                                                                ##STR94##          reddish-tinged yellow                          95   H    --                                                                                ##STR95##          yellow                                         96   5',7'-CH.sub.3                                                                      2 4-SO.sub.2 NH(CH.sub.2).sub.3OC.sub.3                                                              yellow                                         97   5' -C.sub.2 H.sub.5                                                                 1 4-SO.sub.2 NH(CH.sub.2).sub.3OCH.sub.3                                                             yellow                                         98   6',8'-Cl                                                                            2 4-SO.sub.2 NH(CH.sub.2).sub.3OCH.sub.3                                                             yellow                                         99   6',8'-Br                                                                            2 4-SO.sub.2 NH(CH.sub.2).sub.3OCH.sub.3                                                             yellow                                         100  6'-Br                                                                               1 4-SO.sub.2 NH(CH.sub.2).sub.3OCH.sub.3                                                             yellow                                         101  H    --                                                                                ##STR96##          yellow                                         102  H    --                                                                                ##STR97##          golden yellow                                  103  H    --                                                                               3-SO.sub.2 NH(CH.sub.2).sub.3OCH.sub.3                                                             reddish-tinged                                                                 yellow                                         104  H    --                                                                               3-SO.sub.2 NH(CH.sub.2).sub.3OC.sub.2 H.sub.5                                                      reddish-tinged                                                                 yellow                                         105  H    --                                                                               4-SO.sub.2 NH(CH.sub.2).sub.4OCH.sub.3                                                             golden yellow                                  106  H    --                                                                                ##STR98##          golden yellow                                  107  H    --                                                                                ##STR99##          yellow                                         108  H    --                                                                                ##STR100##         golden yellow                                  109  H    --                                                                                ##STR101##         yellow                                         __________________________________________________________________________

EXAMPLE 110

5 parts of 3-hydroxy-quinophthalone-4'-N-ethoxy-propyl-sulphamide (prepared according to Example 88) are suspended in 200 parts of glacial acetic acid and 4.5 parts of bromine are added. The reaction mixture is stirred for 15 hours at room temperature and is then filtered. The residue is washed with bisulphite solution and water, and dried. 5.4 g of the dyestuff of the formula ##STR102## which contains 14.6% of bromine are obtained.

The dyestuff gives yellow dyeings of good fastness properties, especially good fastness to sublimation, also polyester materials.

EXAMPLE 111

1 part of the dyestuff mentioned in Example 87, which has beforehand been brought to a finely divided state in the presence of dispersing agents, is dispersed in 400 parts of water. 100 parts of polyester fibres (polyethylene terephthalate) are dyed in the resulting dyebath in the presence of 15 parts of o-cresotic acid methyl ester as the carrier for 120 minutes at the boil. A strong clear golden yellow dyeing of good fastness properties, especially good fastness to light and sublimation, is obtained.

Clear yellow dyeings which are also strong are obtained if in place of the dyestuff mentioned in Example 87 1 part of the dyestuff obtained in Examples 88, 91, 92, 94, 102, 103, 104 or 105 is employed in the above dyeing procedure.

EXAMPLE 112

100 paerts of polyester fibres (polyethylene terephthalate) are dyed with 1 part of the dyestuff obtained in Example 89, which has beforehand been brought to a finely divided state with the customary auxiliaries, in 3,000 parts of water for one hour at 125°- 130° under pressure. A strong clear yellow dyeing of fastness properties is obtained.

If instead of the dyestuff described in Example 89, 1 part of the dyestuffs described in Examples 88, 93, 95, 96, 97, 106, 107 or 110 is used, clear strong yellow dyeings of good fastness properties, especially of good fastness to sublimation, are again obtained.

EXAMPLE 113

A previously cleaned and thermoset woven fabric of polyethylene terephthalate is printed with a paste consisting of the following components: 20 g of dyestuff obtained according to Example 89, in a finely divided form, 520 g of water, 450 g of 1:2 crystal gum and 10 g of cresotic acid methyl ester. To fix the dyestuff, the printed and dried goods are treated with hot air for 40 seconds at 200°. After soaping, rinsing and drying, a clear golden yellow print of good fastness to light and to sublimation is obtained.

Yellow prints which are also very clear and have good fastness to light and fastness to sublimation are obtained if instead of the abovementioned dyestuff, 20 g of the dyestuffs described in Examples 88, 94, 108 or 110 are used.

EXAMPLE 114

A woven fabric of polyester fibres (polyethylene terephthalate) is impregnated on a padder with a liquor which contains, per liter, 2 g of the dyestuff described in Example 87, which has beforehand been brought to a finely divided state in the presence of dispersing agents. The fabric is squeezed off to a weight pick-up of 70% and is dried at 100°. A strong golden yellow dyeing of good fastness to light, sublimation and rubbing is obtained.

If instead of the abovementioned dyestuff, 20 g of the dyestuffs mentioned in Examples 90, 93, 98, 99, 100 and 101 are used, strong yellow dyeings of good fastness properties, especially good fastness to sublimation, are again obtained.

EXAMPLE 115

100 parts of a polyamide woven fabric are dyed with 1 part of the dyestuff described in Example 87, which has beforehand been brought to a finely divided state in accordance with the customary methods, in 4,000 parts of water for 1 hour at 100°. The fabric is subsequently rinsed warm and cold, and dried. A yellow dyeing of good fastness to washing and to light is obtained.

EXAMPLE 116

A dyebath is prepared with 1 part of the dyestuff mentioned in Example 88, which has beforehand been brought to a finely divided state using the auxiliaries customary for this purpose, 6 parts of fat alcohol-sulphonate and 3,000 parts of water and 100 parts of cellulose triacetate fibres are dyed in this bath for 1 hour at 100°. A yellow dyeing of good fastness to washing, thermosetting and light is obtained. 

We claim:
 1. Water-insoluble quinophthalone dyestuff of the formula ##STR103## wherein ##STR104## Ar is phenyl, naphthyl, mono-, di-, or tri-substituted phenyl, or mono-, di- or tri-substituted naphthyl where the substituents are chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenyl, phenoxy, cyano, nitro, methylmercapto, methoxycarbonyl, or hydroxy;W is oxygen, sulfur, or ##STR105## R is hydrogen, C₁ -C₄ -alkyl, or C₁ -C₄ -alkyl substituted by cyano, hydroxy, methoxy, or chloro; A is straight-chain or branched-chain C₂ -C₆ -alkylene or C₂ -C₆ -alkylene interrupted in its chain by oxygen; R₁ is C₁ -C₄ -alkyl, cyano-C₁ -C₄ -alkyl, hydroxy-C₁ -C₄ -alkyl, methoxy-C₁ -C₄ -alkyl, chloro-C₁ -C₄ -alkyl, phenyl, naphthyl, mono-, di-, or tri-substituted phenyl, or mono-, di-, or tri-substituted naphthyl where the substituents are chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenyl, phenoxy, cyano, nitro, methylmercapto, methoxycarbonyl, or hydroxy; R₂ is hydrogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkyl substituted by cyano, hydroxy, methoxy, or chloro; X is chlorine, bromine, C₁ -C₄ -alkyl, methoxy-C₁ -C₄ -alkyl, chloro-C₁ -C₄ alkyl, C₁ -C₄ -alkoxy, nitro, or C₁ -C₄ -alkylcarbonylamino; Y is halogen, chlorine, or bromine; and n is a number from 0 to
 3. 2. Quinophthalone dyestuff of claim 1 whereinR₁ is C₁ -C₄ -alkyl, phenyl, or phenyl which is mono-, di- or tri-substituted with chloro or methyl; X is chlorine, bromine, C₁ -C₄ -alkoxy, C₁ -C₄ -alkyl, cyano-C₁ -C₄ -alkyl, hydroxy-C₁ -C₄ -alkyl, methoxy-C₁ -C₄ -alkyl, chloro-C₁ -C₄ -alkyl, nitro, or C₁ -C₄ -alkylcarbonylamino; Y is hydrogen or bromine; and n is the number 0, 1, or
 2. 3. Quinophthalone dyestuffs according to claim 1, whereinA represents --(CH₂)_(m) --, X represents Cl, Br, CH₃ or CH₃ O, Y represents H or Br, R₁ represents CH₃ or C₂ H₅, R₂ represents H, CH₃ or C₂ H₅, n represents 0, 1 or 2 and m represents 2, 3 or
 4. 4. Quinophthalone dyestuffs according to claim 1, whereinn represents
 0. 5. Quinophthalone dyestuff according to Claim 1, whereinA represents --C₃ H₆ --, R₁ represents OCH₃, R₂ and Y represent H and n represents O.
 6. Quinophthalone dyestuffs according to Claim 1, whereinT represents W-Ar.
 7. Quinophthalone dyestuffs according to Claim 6, whereinAr represents phenyl, or phenyl which is monosubstituted, disubstituted or trisubstituted by Cl, Br, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, cyano, phenyl or phenoxy, R represents H or C₁ -C₄ -alkyl, Xrepresents Cl, Br, C₁ -C₄ -alkoxy, C₁ -C₄ -alkyl, NO₂ or C₁ -C₄ -alkylcarbonylamino, Y represents H, Cl or Br, n represents 0-2.
 8. Quinophthalone dyestuffs according to claim 7, whereinAr denotes phenyl, chlorophenyl, dichlorophenyl, tolyl, methoxyphenyl, dimethylphenyl and trimethylphenyl, X denotes Cl, Br, CH₃ or CH₃ O, Y denotes H or Br, W denotes O or NR, R denotes H, CH₃ or C₂ H₅ and n denotes 0, 1 or
 2. 9. Quinophthalone dyestuffs according to claim 7, whereinW represents NR. 